1.1 Technical Field
The present invention relates to a novel sodium percarbonate, of overall formula Na2CO3xc2x71.5 H2O2, and to a process for manufacturing it. Sodium percarbonate is also known by the names sodium carbonate sesqui(peroxyhydrate), sodium carbonate peroxyhydrate, or sodium carbonate peroxide.
1.2 Description of The Related Art
The sodium percarbonate known to date is either:
a monocrystal in the form of a hexagonal prism with a density of between 0.9 and 1 g/cm3 (FR 2318112), or
a monocrystal in the form of a regular rhombohedral (FR 2355774), or
a hollow granule with an apparent density of about 0.4 g/cm3 and with an average diameter of about 480 xcexcm (FR 2486056), or
in the form of a compact grain with an average particle size of about 450 xcexcm (BE 859155).
A sodium percarbonate of very high quality, consisting of agglomerated of small crystals, has now been found.
Moreover, it is known to manufacture sodium percarbonate by reaction of a solution or suspension of sodium carbonate with aqueous hydrogen peroxide solution. The addition of inert salts such as sodium chloride to lower the solubility of the sodium percarbonate is also known.
Processes are known for the batchwise manufacture of sodium percarbonate (See, for example, BE 859155 and FR 2368438).
Processes are also known for the continuous manufacture of sodium percarbonate, working either under vacuum (FR 2318112) or with two reactors in series (EP 496430) and leading, respectively, to monocrystals and to crystals of sodium percarbonate less than 75 xcexcm in size.
A process for the continuous manufacture of sodium percarbonate has now been discovered based on the generation and agglomeration of small crystals of the said percarbonate from an aqueous supersaturated solution of sodium percarbonate.
The sodium percarbonate of the present invention consists of agglomerates of small crystals of sodium percarbonate. The size of the small crystals is generally between about 1 xcexcm and about 100 xcexcm and preferably between about 5 xcexcm and about 20 xcexcm. The material of the present invention is characterized by very good resistance to attrition, preferably with a weight loss of fines of less than 1% according to the ISO standard test 5937 (method of friability in a fluid bed).
The sodium percarbonate in agglomerate form according to the invention has an apparent density of greater than about 0.6 g/cm3 and preferably between about 0.75 g/cm3 and about 1.1 g/cm3.
The sodium percarbonate agglomerates of the invention have the advantage of dissolving rapidly. Thus, the time required to obtain 90% dissolution of 2 g of sodium percarbonate agglomerates introduced into one liter of water is generally less than or equal to 90 seconds at 15xc2x0 C. and preferably between 40 and 70 seconds.
The sodium percarbonate in accordance with the invention is formed of agglomerates whose average particle size varies with the conditions chosen to manufacture them.
These conditions, described hereunder, make it possible to obtain agglomerates whose particle size may be between wide limits from about 160 xcexcm to about 1400 xcexcm with a particularly narrow particle size distribution. For example, in the case of agglomerates with an average particle size equal to about 765 xcexcm, generally at least 85% are between about 480 xcexcm and about 1400 xcexcm in size.
Advantageously, the average particle size of these agglomerates is greater than 600 xcexcm and preferably greater than 700 xcexcm.
The content of fines smaller than 160 xcexcm in size present with the agglomerates as obtained from the process which is suitable for manufacturing them is less than 2% by weight, usually even less than 1% by weight.
The active oxygen content of these sodium percarbonate agglomerates is generally greater than 14% and is defined as being the percentage by mass of the amount of oxygen available relative to the sodium percarbonate agglomerates.
A second subject of the present invention is a process for the continuous manufacture of sodium percarbonate in the form of agglomerates consisting of small crystals and having at least one of the characteristics described above.
This process is characterized in that it comprises a reactor within which is a bed of small crystals and/or agglomerates of sodium percarbonate. A supersaturated solution of sodium percarbonate is formed by placing a suspension or solution of sodium carbonate in contact with an aqueous hydrogen peroxide solution. The bed is maintained in suspension by an ascending stream of the aqueous supersaturated solution of the said percarbonate. The supersaturated state of the aqueous solution decreases as it moves in a continuously ascending motion at a speed such that a desired particle-size classing of agglomerates is ensured.
In general, the process for producing sodium percarbonate agglomerates according to the present invention comprises the following steps:
a) forming an aqueous supersaturated solution of sodium percarbonate in a reactor by placing a suspension or a solution of sodium carbonate in contact with an aqueous hydrogen peroxide solution,
b) charging the reactor with a bed of sodium percarbonate, wherein the sodium percarbonate is present in the form of small crystals, agglomerates, or mixtures thereof, and
c) maintaining the bed of sodium percarbonate in suspension by contacting the bed with an ascending stream of the aqueous supersaturated solution of sodium percarbonate, wherein the solution forms a stream which ascends in a path and the linear ascending speed of the stream is between 2 m/h and 20 m/h.
The sodium percarbonate agglomerates thusly manufactured are removed from the suspension in the lower part of the bed.
At the end of its ascending movement, the aqueous solution is supersaturated with sodium percarbonate and has a sodium percarbonate concentration generally between the value corresponding to the solubility of sodium percarbonate in the same medium at the same temperature and about 1.6 times that value. At the end of its ascending motion, the aqueous solution preferably has a sodium percarbonate concentration of between about 1 and about 1.4 times the value corresponding to the solubility of sodium percarbonate in the same medium at the same temperature. The amount of solid material present at this level in the reactor is generally less than 150 g per liter of aqueous solution and preferably between about 10 and about 25 g per liter of aqueous solution.
In order to form the sodium percarbonate needed to ensure the supersaturated state of the aqueous supersaturated solution of sodium percarbonate, amounts of hydrogen peroxide and of sodium carbonate are used such that the molar ratio of hydrogen peroxide to sodium carbonate dissolved in the mother liquor, at the end of the ascending motion of the aqueous supersaturated solution, is greater than 1 and preferably between about 1.2 and about 1.6.
The supplying of sodium percarbonate as an aqueous solution to ensure this supersaturated state may be performed by formation of the said percarbonate in the aqueous supersaturated solution of percarbonate itself or outside this solution. The formation of sodium percarbonate in the aqueous supersaturated solution of sodium percarbonate is particularly preferred and it is performed by continuous introduction of aqueous hydrogen peroxide solution and of a suspension or solution of sodium carbonate, optionally containing sodium percarbonate in solution or suspension. Preferably, the aqueous hydrogen peroxide solution is introduced into the ascending path of the aqueous supersaturated solution of sodium percarbonate at a level very close to the zone of introduction of the sodium carbonate suspension or solution. The introductions of the aqueous hydrogen peroxide solution and of the sodium carbonate suspension or solution may also take place at several levels.
Preferably, the sodium carbonate suspension or solution is introduced into the zone between the level located at the upper limit of removal of the agglomerates and the level located at about the midpoint of the ascending path of the supersaturated solution of sodium percarbonate.
The concentration in the supersaturated state of the aqueous sodium percarbonate solution in the zone of introduction of the hydrogen peroxide solution and of the sodium carbonate suspension or solution is normally greater than 1.2 times the value of the solubility of the sodium percarbonate in this same medium at the same temperature. It is preferably between about 1.3 and about 6 times that value.
Crystals and/or agglomerates of sodium percarbonate may be generated in the presence of at least one crystallization agent. The agent may be introduced at one or more levels in the ascending path of the aqueous supersaturated solution of sodium percarbonate. These levels are preferably located in the zone of introduction of the aqueous hydrogen peroxide solution and of the sodium carbonate suspension or solution and/or above this zone. Among the crystallization agents, sodium hexametaphosphate is particularly preferred. The amount of crystallization agent or agents used is such that their concentration in the aqueous supersaturated solution of sodium percarbonate is greater than 0.1 g/l and is usually between about 0.5 g/l and about 2.7 g/l.
An anionic surfactant may also be used to control the crystallization of the sodium percarbonate. At least one surfactant is preferably introduced at the level of the zone of introduction of the sodium carbonate suspension or solution. Anionic surfactants containing at least one sulfate or sulphonate function attached to a hydrocarbon chain are particularly preferred. The amount of surfactant or surfactants used is such that their concentration in the mother liquor is greater than 0.1 g/l and is usually between about 0.7 g/l and about 1 g/l. Isobutyl oleate sulfate is advantageously chosen among the surfactants.
To lower the solubility of the sodium percarbonate, at least one release agent such as a sodium salt may also be used. Sodium chloride is particularly preferred. The amount of release agent or agents used is such that their concentration in the mother liquor is greater than 20 g per liter and preferably between about 70 g/l and about 170 g/l.
The continuous introduction of hydrogen peroxide into the solid-liquid suspension is ensured by an aqueous hydrogen peroxide solution with a concentration by weight of between about 35% and about 70%. The aqueous hydrogen peroxide solution may also contain sodium carbonate, a stabilizer, in particular, sodium silicate or magnesium sulfate, and a release agent, such as sodium chloride.
The continuous introduction of sodium carbonate into the solid-liquid suspension is ensured by an aqueous concentrated suspension or solution of sodium carbonate, the titre of which is greater than 10% and preferably between about 15% and about 24%, optionally containing sodium percarbonate in solution or in suspension. The concentrated sodium carbonate solution may be prepared by dissolving commercial sodium carbonate in water or in some or all of the solution taken from the solid-liquid suspension at the end of its ascending motion, at a temperature above 17xc2x0 C. The dissolution temperature is preferably between about 30xc2x0 C. and about 70xc2x0 C.
Any type of sodium carbonate having an iron (Fe) content of less than 10 ppm may be suitable. Anhydrous sodium carbonate obtained from Solvay or Rhxc3x4ne-Poulenc is preferably used.
The concentrated suspension or solution of sodium-carbonate may also contain stabilizers such as, in particular, sodium silicate or magnesium sulfate, release agents such as sodium chloride and crystallization agents such as sodium hexametaphosphate.
The stirred state of the solid-liquid suspension during the ascent of the liquid is ensured by a paddle-stirrer, a propeller-stirrer or a stirrer in the form of a stepladder. This stirring must be conducted such that the actual state of suspension and the particle size classing effect are maintained. Furthermore, stirring must be conducted such that the small crystals of sodium percarbonate are maintained in a position of contact or in a proximity which is sufficient for them to agglomerate.
The linear ascending speed of the liquid in the cylindrical part of the reactor may be between about 2 m/h and about 20 m/h. A linear ascending speed of between about 3 m/h and about 10 m/h is advantageously used. The expression xe2x80x9clinear ascending speedxe2x80x9d is understood to refer to the ratio of the fluidization volumetric flow rate to the cross-sectioned area of the reactor.
The temperature of the solid-liquid suspension is between about 14xc2x0 C. and about 20xc2x0 C. It is adjusted with precision using one or more heat exchangers in parallel. A temperature of the solid-liquid suspension of about 17xc2x0 C. is particularly preferred and it is advantageously controlled to within xc2x11xc2x0 C.
At the end of the ascending motion of the solid liquid suspension, the solid material may optionally be separated from the liquid by standard techniques such as settling, filtration, centrifugation or by using a hydrocyclone.
Some or all of this liquid (optionally separated from solid material) and, optionally, added water, constitute the liquid flow entering the bottom of the reactor in which the agglomerates according to the invention are formed.
According to the process of the present invention, a column reactor or a reactor of cylindroconical shape which is optionally fitted with a small neck in its upper part may be used. A cylindroconical reactor is usually used. Preferably, a cylindroconical reactor fitted with a small neck is used.